Dyeing carriers and their use



United States Patent 3,057,674 DYEiNG CARQZE'RS AND THEE USE David M.Musser, Fair Lawn, and John H. Veileiiarup, Tenaiiy, Ni, assignors toChicopee Manufacturing Qcrporation, a corporation of Massachusetts NoDrawing. Filed Jan. 12, 1960, Ser. No. 1,880 7 (Claims. (Cl. 8-83) Thepresent invention relates to improved methods of dyeing hydrophobic,synthetic organic materials in the form of fibers, fabrics and shapedarticles, and to novel compositions for use therein.

Within recent years, the number of synthetic materials, especially infiber form, which have been developed and offered for commercialacceptance has increased many fold. Typical of such materials are thepolyester fibers, such as Dacron, Kodel, Vycron, Terylene and Teron; thecellulose triacetate fibers such as Arnel and Tricel; the acrylic fiberssuch as Acrilan and Creslan; and so forth.

Such hydrophobic materials cannot be satisfactorily dyed by the ordinarydyeing procedures previously used for dyeing cotton, wool, silk,regenerated cellulose, and the like. When such ordinary dyeingprocedures are used for dyeing hydrophobic synthetic organic materials,the dye does not penetrate the materials and either no dyeing isobtained or, if some measure of dyeing is obtained, the color is notfast and washes out of the materials. As a result, the dyeing of suchhydrophobic materials is presently effected by other methods such as,for example, by being carried out in the presence of a swelling agentwhich forms or opens the pores of the hydrophobic materials and permitsthe dye to enter and remain there in a colorfast manner.

Very many chemical compounds and compositions have been developed asassistants or carriers for the dyeing of hydrophobic materials. Many ofthese are phenols or phenolic derivatives which are acidic and corrosivein nature and consequently are not completely satisfactory or acceptableto industry. Additionally, these phenolics decrease light fastness andintroduce persistent objectionable odors during the dyeing process whichoften remain in the dyed materials after dyeing. Other dyeing carriercompositions have also been toxic of irritating, or have been lexpensiveand uneconomical, and accordingly also are not completely satisfactoryor acceptable to industry.

Another objectionable feature of prior art carriers is noted in that inmany cases, when it was desired to make additions either of more dye ormore dyeing carrier to heated dyeing compositions during dyeingoperations, in order to obtain or match various shades, it was necessaryto cool the heated dyeing composition before such additions could bemade. Such cooling and subsequent reheating to dyeing temperatures toresume dyeing operations was time consuming and costly and consequentlyobjectionable.

A new dyeing carrier composition has now been discovered and developedwhich is non-phenolic in nature, is not toxic or irritating, hasexcellent light fastness, and does not introduce any objectionable odorsduring dyeing or subsequent use. Furthermore, additions may be made toheated dyeing compositions containing such a carrier at elevatedtemperatures without cooling, as previously required.

Such an improved dyeing carrier composition comprises trichlorobenzeneand a select combination of emulsifying agents which are employed inspecified proportions with respect to one another and to thetrichlorobenzene whereby the desired abovementioned results areobtained.

The term trichlorobenzene, as used herein, is intend ed to cover any oneof th isomeric forms of trichlorobenice.

zene, or any combination or mixture of the same in any proportion. 1,2,3trichlorobenzene (vic trichlorobenzene) and 1,2,4-trich1orobenzene(asym-trichlorobenzene), and especially mixtures of the same, arepreferred due to the ready commercial availability thereof but such isnot intended to exclude the use of 1,3,5-trichlorobenzene(sym-trichlorobenzene).

The select combination of emulsifying agents comprises, as a firstingredient, a monovalent salt of a sulfated alkyl polyether alcohol.Such an emulsifying agent is obtained by treating a long chain aliphaticalcohol containing from 8 to 18 carbon atoms, and preferably from 10 to14 carbon atoms, with an alkylene oxide, preferably ethylene oxide, andthen treating the resulting alkyl polyether alcohol with concentratedsulfuric or sulfamic acid to sulfate the same, and subsequentlyneutralizing the sulfated alkyl polyether alcohol to yield the desiredemulsifying agent.

The long chain aliphatic alcohol containing from 8 to 18 and preferablyfrom 10 to 14 carbon atoms may possess a relatively straight alkyl chainsuch as when derived from nut oils. Coconut, babassu, and palm kerneloil having a low iodine value and containing a high percentage of almost50% saturated twelve carbon atom alcohols and a substantial percentageof saturated fourteen carbon atom alcohols are particularly applicable.Other oils suitable for the purposes of the present invention are cohuneoil, ouricuri oil, murumuru oil, and tucu-m oil. The mixture ofisomeric, highly branched chain tridecyl alcohols such as obtained bythe 0x0 process is similarly particularly applicable.

The extent of the treatment of the alcohol with ethylene oxide may bevaried within relatively Wide limits depending upon the degree of thehydrophilic properties desired. The Emulphogene series of nonionicemulsifiers are examples of such alkyl polyethyleneoxy alcohols whereinthe degree of hydrophilic properties is increased as the number of molesof ethylene oxide incorporated in the alcohol is increased. For thepurposes of the present invention, the introduction of from about 2 toabout 30 moles of ethylene oxide in the alcohol has been foundsatisfactory, with from about 3 to about 10 moles being preferred.

The alkyl polyethyleneoxy alcohols are then sulfonated (actuallysulfated) by treatment with concentrated sulfamic or sulfuric acid byprocedures well known to industry.

Subsequent to the treatment of the alkyl polyethyleneoxy alcohol withthe sulfamic or sulfuric acid, neutralization is effected by treatmentwith a base, such as ammonia or an alkali metal hydroxide or carbonate,or the like. As a consequence, the final emulsifier is a monovalent saltof a strong acid, is more resistant to hard water, and is more stable inaqueous solutions of low pH.

The second ingredient of the select combination of emulsifying agents isobtained by treating an unsaturated animal, fish or vegetable fat oroil, preferably tallow, sperm oil or castor oil, with a sulfating agentsuch as sulfuric or sulfamic acid. The resulting product, althoughfrequently referred to as sulfonated is actually sulfated and containsthe -OSO H radical or a salt thereof, such as the ammonium salt, i.e.,-OSO NH Although sulfonated tallow, sperm oil and castor oil are used indescribing the applicability of the present inventive concept, it is tobe appreciated that other sulfonated animal, fish or vegetable fats oroils are utilizable. Illustrative of other unsaturated fats and oilssuitable for use in the present inventive concept are: peanut oil; rape(rapeseed) oil; olive oil; palm oil; neats-foot oil; teaseed oil; almondoil; apricot kernel oil; etc.

As used herein, the term anima naturally refers to land animals and theterm fish is intended to indicate a marine origin and includes aquaticmammals, notably the whale.

As used herein, the term unsaturated fat or oil is intended to coverthose fats or oils containing at least about 40% by weight ofunsaturated monoenoic acids, notably oleic acid, and normally greaterthan about 60% by weight of unsaturated monoenoic acids. Suchunsaturated fats and oils have iodine values in excess of about 30, andoften in excess of about 80, but not substantially in excess of about115, at which point their drying characteristics, due usually to thepresence of higher percentages of dienoic acids, notably linoleic acid,would begin to interfere with the application of the present inventiveconcept. Modified fats and oils, for example, those prepared byhydrogenation processes, are suitable for the purposes of the presentinvention provided their properties and characteristics are as describedherein.

In the dyeing carrier compositions, the ranges of the relativeproportions of the trichlorobenzene, the monovalent salt of the sulfatedalkyl polyether alcohol, and the sulfonated animal, fish or vegetablefat or oil may be varied within relatively wide limits. For example, thedyeing carrier composition may comprise from about 40 parts to about 80parts by Weight of the trichlorobenzene, from about 2 parts to about 30parts by weight of the monovalent salt of the sulfated alkyl polyetheralcohol, and from about 6 parts to about 40 parts by Weight of thesulfonated animal, fish, or vegetable fat or oil. On a percentage byWeight basis, the following proportions have been found optimum: fromabout 55% to about 75% by weight of the trichlorobenzene; from about 4%to about 20% by weight of the monovalent salt of the sulfated alkylpolyether alcohol; and from about 11% to about 35% by Weight of thesulfonated animal, fish or vegetable fat or oil.

The amount of the dyeing carrier composition to be added to the dye bathmay be varied within relatively Wide limits and depends primarily uponthe dry weight of the hydrophobic synthetic materials being dyed. Withinthe broader aspects of the present invention, from about 1% to about 12%by weight of the dyeing carrier, based on the dry weight of thehydrophobic synthetic materials has been found satisfacotry, Within themore commercial aspects of the present invention, from about 1 /2 toabout has been found preferable, with optimum values being noted in therange of from about 2% to about 8% by Weight.

The invention will be further illustrated in greater detail by thefollowing specific examples. It should be understood, however, thatalthough these examples may describe in particular detail some of themore specific features of the invention, they are given. primarily forpurposes of illustration and the invention in its broader aspects is notto be construed as limited thereto.

Example I The dyeing carrier is prepared from: 65 parts by Weight oftrichlorobenzene (technical grade; mixture of 1,2,4- and1,2,3-trichlorobenzene, with 1,2,4- predominating); 15 parts by Weightof the ammonium salt of sulfated tridecyl polyethyleneoxy ethanol (60%active); and parts by weight of sulfonated castor oil (75% concentratedsolution). Analysis of the alcohol reveals the treatment with about 4moles of ethylene oxide. The castor oil used analyzes 0.3% stearic acid,8.0% oleic acid, 87.8% ricinoleic acid, and 3.6% linoleic acid. Itsiodine value is 85.

The resulting product is a light amber-colored liquid which isself-dispersible in warm water and is compatible with anionic dyeingassistants, detergents and sequestrants. Its pH (1% solution) is neutraland it has excellent storage stability and shelf-life. The dyeingcarrier is dispersed in water at 160 F. (71 C.) and is thoroughlystirred to yield a milk-blue colored stable emulsion.

A fabric woven from Dacron polyester fibers is prepared for dyeing bythorough scouring and cleaning to remove lay marks, oxidized stains andother soil. The fabric goods are loaded and a small amount (about 0.1%)of an anionic dyeing assistant and enough sequestering agent (tetrasodium salt of ethylene diamine tetra acetic acid) is added to softenthe water. The temperature of the bath is raised to F. (49 C.). Thedyeing carrier is run into the dye bath in an amount equal to 7%, basedon the dry weight of the Dacron polyester fabric, With the temperatureof the bath being maintained at 120 F. (49 C.). The dye is then added inthe amount desired and the temperature of the bath is raised close tothe boil and maintained at that temperature until the desired shade isobtained. The dyedgoods are rinsed in water at F. (54 C.). Noobjectionable, irritating or toxic odors are noticed at any time duringthe dyeing process. The dyeing carrier promotes deep penetration of thedye and prevents bleeding on wet pressing and processing. The dyeing isuniform and level. No objectionable, irritating or toxic odors aredeveloped during subsequent use of the dyed fabric. Its light fastnessis excellent.

Example II The procedures of Example I are followed substantially as setforth therein except that the amount of the dye is deliberately reducedso that it is insulficient to yield the desired shade when the dye bathis brought close to the boil. An additional amount of dye is added,without cooling the dye bath, and the desired shade is obtained. Theproperties of the dyed fabric are similar to those obtained in the dyedfabric of Example I.

Example III The procedures of Example I are followed substantially asset forth therein except that a fabric Woven from Acrilan acrylic fibersis used. The amount of dyeing carrier used is reduced to 4%, based onthe dry weight of the fabric. The results are satisfactory and arecomparable to the results obtained in Example I.

Example IV The procedures of Example I are followed substantially as setforth therein except that a fabric woven from Arnel cellulose triacetatefibers is used. The amount of dyeing carrier used is reduced to 2%,based on the dry Weight of the fabric. The results are satisfactory andare comparable to the results obtained in Example I.

Example V The procedures of Example I are followed substantially as setforth therein except that the percentage of the constituents of thedyeing carrier is changed to: 40 parts by weight of trichlorobenzene; 5parts by weight of the sodium salt of sulfated tridecyl polyethyleneoxyethanol (60% active); and 10 parts by weight of sulfonated castor oil(75%). About 8% by weight of this carrier is used, based on the dryweight of the fabric being dyed. The results are satisfactory and arecomparable to those obtained in Example I.

Example VI The procedures of Example I are followed substantially as setforth therein except that the percentage of the constituents of thedyeing carrier is changed to: 80 parts by Weight of trichlorobenzene; 25parts by weight of the sodium salt of sulfated tridecyl polyethyleneoxyethanol (60% active); and 40 parts by Weight of sulfonated castor oil(75%). About 5% by Weight of this carrier is used, based on the dryweight of the fabric being dyed. The results are satisfactory and arecomparable to those obtained in Example I.

Example VII The procedures of Example I are followed substantially asset forth therein except that sulfonated sperm oil is used to replacethe sulfonated castor oil. The sperm oil prior to its treatment with theconcentrated sulfuric acid, analyzes 8.0% myristic acid, 12.1% palmiticacid, 2.3% stearic acid, 1.5% C -unsaturated acid, 15.0% palmitoleicacid, 33.4% oleic acid, 18.7% C and C -unsaturated acids, and 9%linoleic acid. Its iodine value is 110. The dyeing carrier isself-emulsifiable in water and yields a uniform stable emulsion.

Example VIII The procedures of Example I are followed substantially asset forth therein except that the ammonium salt of sulfated tridecylpolyethyleneoxy ethanol is replaced by the ammonium salt of sulfatedlauryl polyethyleneoxy alcohol (also 60% active). Lauryl alcohol is thestarting alcohol; about 4 moles of ethylene oxide are added to thealcohol nucleus; and sulfamic acid is the sulfonating agent. The dyeingcarier disperses easily in water and yields a stable emulsion.

Example IX The procedures of Example I are followed substantially as setforth therein except that sulfonated beef tallow is used to replace thesulfonated castor oil. The beef tallow, prior to its sulfonation withconcentrated sulfuric acid, analyzes 0.2% lauric acid, 3.1% myristicacid, 24.9% palmitic acid, 24.1% stearic acid, 41.8% oleic acid, 2.4%palmitoleic acid, and 1.8% lino-leic acid. Its iodine value is 44. Thedyeing carrier is readily selfdispersible in water and yields a uniformstable emulsion.

Although several specific examples of the inventive concept have beendescribed, the same should not be construed as limited thereby nor tothe specific features mentioned therein but to include various otherequivalent features as set forth in the claims appended hereto. It isunderstood that any suitable changes, modifications and variations maybe made Without departing from the spirit and scope of the invention.

What is claimed is:

1. A dyeing carrier for use in dyeing hydrophobic, synthetic organicmaterials comprising from about 40 to about 80 parts by weight oftrichlorobenzene, from about 2 parts to about 30 parts by weight of awater soluble monovalent salt of a sulfated alkyl polyether alcoholderived from a long chain aliphatic alcohol containing from 8 to 18carbon atoms, and from about 6 parts to about 40 parts of a member ofthe group consisting of sulfonated animal, fish and vegetable fats andoils, and mixtures thereof.

2. A dyeing carrier for use in dyeing hydrophobic, synthetic organicmaterials comprising from about 40 to about parts by weight oftrichlorobenzene, from about 2 parts to about 30 parts by weight of awater soluble monovalent salt of a sulfated alkyl polyether alcoholderived from a long chain aliphatic alcohol containing from 8 to 18carbon atoms, and from about 6 parts to about 40 parts of a sulfonatedanimal fat.

3. A dyeing carrier for use in dyeing hydrophobic, synthetic organicmaterials comprising from about 40 to about 80 parts by weight oftrichlorobenzene, from about 2 parts to about 30 parts by weight of awater soluble monovalent salt of a sulfated alkyl polyether alcoholderived from a long chain aliphatic alcohol containing from 8 to 18carbon atoms, and from about 6 parts to about 40 parts of a sulfonatedtallow.

4. A dyeing carrier for use in dyeing hydrophobic, synthetic organicmaterials comprising from about 40 to about 80 parts by weight oftrichlorobenzene, from about 2 par-ts to about 30 parts by weight of aWater soluble monovalent salt of a sulfated alkyl polyether alcoholderived from a long chain aliphatic alcohol containing from 8 to 18carbon atoms, and from about 6 parts to about 40 parts of a sulfonatedfish oil.

5. A dyeing carrier for use in dyeing hydrophobic, synthetic organicmaterials comprising from about 40 to about 80 parts by weight oftrichlorobenzene, from about 2 parts to about 30 parts by weight of awater solu ble monovalent salt of a sulfated alkyl polyether alcoholderived from a long chain aliphatic alcohol containing from 8 to 18carbon atoms, and from about 6 parts to about 40 parts of a sulfonatedsperm oil.

6. A dyeing carrier for use in dyeing hydrophobic, synthetic organicmaterials comprising from about 40 to about 80 parts by Weight oftrichlorobenzene, from about 2 parts to above 30 parts by Weight of awater soluble monovalent salt of a sulfated alkyl polyether alcoholderived from a long chain aliphatic alcohol containing from 8 to 18carbon atoms, and from about 6 parts to above 40 parts of a sulfonatedvegetable oil.

7. A dyeing carrier for use in dyeing hydrophobic, synthetic organicmaterials comprising from about 40 to about 80 parts by weight oftrichlorobenzene, from about 2 parts to about 30 parts by weight of awater soluble monovalent salt of a sulfated alkyl polyether alcoholderived from a long chain aliphatic alcohol containing from 8 to 18carbon atoms, and from about 6 parts to about 40 parts of a sulfonatedcastor oil.

References Cited in the file of this patent UNITED STATES PATENTS2,880,050 Fortess Mar. 31, 1959 FOREIGN PATENTS 581,244 Canada Aug. 11,1959 812,362 Great Britain Apr. 22, 1959 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3,057,674 Q October 9 1962 David M.Musser et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1, line 44, for "of" read 0r line 71, for "th" read the column 5line 31, for lino-=1eic" read linoleic column 6 lines 34 and 37, for"above" each occurrence, read about Signed and sealed this 26th day ofMarch 19630 (SEAL) Attest:

ESTON G. JOHNSON DAVID L. LADD Attesting Officer Commissioner of Patents

1. A DYEING CARRIER FOR USE IN DYEING HYDROPHOBIC, SYNTHETIC ORGANICMATERIALS COMPRISING FROM ABOUT 40 TO ABOUT 80 PARTS BY WEIGHT OFTRICHLOROBENZENE, FROM ABOUT 2 PARTS TO ABOUT 30 PARTS BY WEIGHT OF AWATER SOLUBLE MONOVALENT SALT OF A SULFATED ALKYL POLYETHER ALCOHOLDEREIVED FROM A LONG CHAIN ALIPHATIC ALCOHOL CONTAINING FROM 8 TO 18CARBON ATOMS, AND FROM ABOUT 6 PARTS TO ABOUT 40 PARTS OF A MEMBER OFTHE GROUP CONSISTING OF SULFONATED ANIMAL, FISH AND VEGETABLE FATS ANDOILS, AND MIXTURES THEREOF.